Modulating the Electronic Structures of Dual‐Atom Catalysts via Coordination Environment Engineering for Boosting CO2Electroreduction

Abstract Dual‐atom catalysts (DACs) have emerged as efficient electrocatalysts for CO 2 reduction owing to the synergistic effect between the binary metal sites. However, rationally modulating the electronic structure of DACs to optimize the catalytic performance remains a great challenge. Herein, we report the electronic structure modulation of three Ni 2 DACs (namely, Ni 2 −N 7 , Ni 2 −N 5 C 2 and Ni 2 −N 3 C 4 ) by the regulation of the coordination environments around the dual‐atom Ni 2 centres. As a result, Ni 2 −N 3 C 4 exhibits significantly improved electrocatalytic activity for CO 2 reduction, not only better than the corresponding single‐atom Ni catalyst (Ni−N 2 C 2 ), but also higher than Ni 2 −N 7 and Ni 2 −N 5 C 2 DACs. Density functional theory (DFT) calculations revealed that the high electrocatalytic activity of Ni 2 −N 3 C 4 for CO 2 reduction could be attributed to the electronic structure modulation to the Ni centre and the resulted proper binding energies to COOH* and CO* intermediates.